SEARCH · Engineering Papers

Results for “INTERMEDIATE COUPLING”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,639 records · Page 91

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Development of an in situ dual-channel thermal desorption gas chromatography instrument for consistent quantification of volatile, intermediate-volatility and semivolatile organic compounds

Abstract. Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood health impacts. Most aerosol mass is formed in the atmosphere from reactive gas-phase organic precursors, forming secondary organic aerosol (SOA). Semivolatile organic compounds (SVOCs) (effective saturation concentration, C*, of 10−1–103 µg m−3) comprise a large fraction of organic aerosol, while intermediate-volatility organic compounds (IVOCs) (C* of 103–106 µg m−3) and volatile organic compounds (VOCs) (C* ≥ 106 µg m−3) are gas-phase precursors to SOA and ozone. The Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) is the first single instrument simultaneously quantitative for a broad range of compound-specific VOCs, IVOCs and SVOCs. cTAG is a two-channel instrument which measures concentrations of C5–C16 alkane-equivalent-volatility VOCs and IVOCs on one channel and C14–C32 SVOCs on the other coupled to a single high-resolution time-of-flight mass spectrometer, achieving consistent quantification across 15 orders of magnitude of vapor pressure. cTAG obtains concentrations hourly and gas–particle partitioning for SVOCs every other hour, enabling observation of the evolution of these species through oxidation and partitioning into the particle phase. Online derivatization for the SVOC channel enables detection of more polar and oxidized species. In this work we present design details and data evaluating key parameters of instrument performance such as I/VOC collector design optimization, linearity and reproducibility of calibration curves obtained using a custom liquid evaporation system for I/VOCs and the effect of an ozone removal filter on instrument performance. Example timelines of precursors with secondary products are shown, and analysis of a subset of compounds detectable by cTAG demonstrates some of the analytical possibilities with this instrument.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1981

Nucleocosmochronology

Nucleocosmochronology is analyzed on the basis of elemental isotopic abundances of radionuclides. The production and depletion mechanisms for the cosmological chronometers are investigated and model-independent theories are reviewed. Emphasis is given to the significance of the mean age of the elements and the time resolution of the last nucleosynthetic events contributing to the solar system, and it is shown how the intermediate-lived chronometers may give information on the time dependence shape of the production function. Anomalous nucleocosmochronology is investigated and galactic and cosmological constraints are described in terms of time scales for the mean age of elements and galaxies and the age of the universe. Data resulting from both model-independent and dependent analyses are compared. Results based on the mean age for the r-process elements suggest a lower limit to the age of the galaxy and the universe. It is concluded that nucleocosmochronology, when coupled with other independent determinations for the age of the universe, defines a concordant universe age of 13.5-15.5 billion years. The shape of the production function is not well determined because of the uncertainties in the xenon data.

Symbalisty, E. M. D.↗

DOE OSTI2016

Innovative Waste Packaging and Associated Venting/Hydrogen Management - 16594

The original strategy for managing intermediate level waste (ILW) was developed in the 1980s by the UK Nuclear Industry Radioactive Waste Executive (NIREX), which is now the Radioactive Waste Management Limited (RWM), a wholly owned subsidiary of the Nuclear Decommissioning Authority (NDA). The strategy involved retrieving ILW, sorting and encapsulating it in cement based grout within thin walled stainless steel containers. The containers would then be transferred to a large purpose-built shielded ILW store on site, where they would be stored until the planned final deep geological disposal facility becomes available. In recognition of the high up-front costs of such a strategy, which requires remote facilities for the encapsulation and storage, and coupled with the long programme duration for the design, construction and commissioning of these facilities, waste management organisations responsible for managing the clean-up of legacy facilities within the UK have, in recent years, sought innovative solutions which could potentially both accelerate clean-up and hazard reduction on sites, and with a lower overall programme lifecycle cost. Many of the recent innovative solutions are focused around a new family of packaging designs known as robust shielded containers (RSCs). These are self-shielded containers manufactured from materials such as ductile cast iron or fabricated steel. These containers offer the potential to package wastes for disposal without encapsulation and avoid the need for a highly engineered remote handled shielded store for interim storage. The paper provides a high level overview of the generic concepts of RSCs developed by Croft and focuses on the specific challenges of wasteform evolution on waste package integrity and performance. In particular, the integrity and performance of the filtered vent system required to manage internal pressurisation and to ensure sufficient venting capacity of hydrogen and other evolved gases. The paper summarises the analysis by ARUP undertaken to substantiate the RSC integrity under detonation/deflagration explosion loadings arising from hydrogen accumulation. Analyses of the structural response of the filter assembly were undertaken for both detonation and deflagration explosion scenarios, with the loadings applied to the filter housing rim and to the filter vent cover. The paper also presents evidence of the mechanical performance of the filter medium in terms of pressure transients during deflagration events and the degree to which filtration efficiency is maintained. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Optimizing feed modulation for coupled methane and NO x conversion over Pd-Pt/Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith catalyst

Here the impacts of feed modulation (frequency, amplitude) and catalyst design (composition and architecture) parameters are reported for the conversion of methane and NO x over a dual-layer Pt+Pd/Al 2 O 3 + Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith. CH 4 and NO x conversion data show that the dual-layer catalyst outperforms single-layer samples having the same catalyst loadings, with and without spinel. Close proximity of the PGM and MFO functions in the mixed-layer catalyst lowers the CH 4 conversion at high temperature while separating the PGM and spinel layers with an intermediate Al 2 O 3 layer does not. Methane conversion enhancement is linked to its nonmonotonic dependence on O 2 . The performance gains are tied to a transient activity spike that occurs during the lean-to-rich feed transition when water is present in the feed. The transient spike is attributed to the removal of CO and H 2 products via reactions with stored O 2 in the spinel, eliminating inhibition of methane steam reforming.

03 NATURAL GAS↗

DOE OSTI2022

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High–Performance Carbon Dioxide Electroreduction

The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO 2 reduction reaction (CO 2 RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO 2 -to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO 2 RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm –2 with CO Faradaic efficiency of >95% at –0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. Finally, this work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Coupled CFD and chemical-kinetics simulations of cellulosic-biomass enzymatic hydrolysis: Mathematical-model development and validation

Computational simulations of cellulosic-biomass enzymatic hydrolysis using a computational-fluid-dynamics (CFD) model coupled to a chemical-kinetics model are presented in this work. A time-step sub-cycling strategy was used to circumvent large disparities in time scales with respect to transport physics and chemical kinetics. The unknown reaction and transport parameters in the mathematical model were first fit to two canonical experiments: a well-mixed case that was limited by reaction kinetics and a settled-solids case that was limited by transport. Here, the model was then validated against a benchtop experiment for an intermediate-mixing scenario, for which simulation results were in reasonable agreement with experimentally measured cellulose conversions. Settling of cellulose particles and diffusion of enzymes determine overall conversion rates for lower mixing rates, while reaction rates dominate conversion at higher mixing rates for which greater homogenization of substrates is achieved.

09 BIOMASS FUELS↗

DOE OSTI2026

C–C Bond Formation during Electrochemical CO 2 Reduction on Pristine Cu(100) Unlikely to Involve Adsorbed CO at Any Potential

Formation of hydrocarbons containing two or more carbon atoms (C 2+ ) during heterogeneous electrochemical CO and CO 2 reduction (ECOR and ECO 2 R) only occurs, among pure metals, on Cu electrodes. Moreover, the activity and selectivity is facet dependent, with Cu(100) generally preferentially forming ethylene over methane. Previously, we found via quantum-mechanics-based modeling that, unlike standard density functional theory, more accurate correlated wavefunction methods predict that non-electroactive coupling pathways involving two adsorbed COs (*CO) or a *CO and a *COH to form C–C bonds on Cu(100) are kinetically inhibited, with the former also thermodynamically unfavorable. Here, we extend that embedded complete active space second order perturbation theory (ECASPT2) study, further showing that electrochemical coupling of two *COs to form an anionic dimer [OC*–*CO] (1+δ)– , followed by protonation to form [OC*–*COH] δ− , is not kinetically competitive with the reduction of *CO to *COH at relevant ECO/CO 2 R potentials. Our simulations therefore suggest that the ability of Cu(100) to electrochemically synthesize C 2+ molecules from CO and CO 2 is unlikely to be via *CO, at least on pristine Cu(100). Instead, hydrogenated CO species (*COH, *CH x OH, or *CH x ) are most likely to be the key intermediates in C–C bond formation.

Martirez, John Mark P. [Princeton Plasma Physics L↗

DOE OSTI2025

Impact of Pendant Amine Basicity on Electrochemically-Promoted Cobalt Hydride Formation: Kinetic and Mechanistic Analysis

Here, we report the role of pendant amine basicity on the proton-coupled electron transfer (PCET) reactivity for the conversion of [Co III Cp(P Ph 2 N R 2 )(CH 3 CN)] 2+ complexes to [HCo III Cp(P Ph 2 N R 2 )] + , which is a key transformation involved in catalytic CO 2 conversion to formate and in H 2 evolution. Three complexes were studied, where the amine substituent (R) varies from benzyl, methoxyphenyl, or phenyl. In previous work on the benzyl system, we showed that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site and enables three participating hydride formation mechanisms. In this work, a combination of electrochemical measurements and theoretical calculations were used to show that the electronic donation at the pendant amine influences the accessible PCET mechanism and proton transfer kinetics related to cobalt hydride formation under analogous reaction conditions. Notably, the amine with the most electron-donating substituent correlates to the lowest barrier for amine protonation, and specific cobalt hydride formation mechanisms can be shut off for the amine with the least electron-donating substituent. The mechanistic and kinetic changes upon modulation of the amine substituent have great implications for overall catalytic efficiency and selectivity, especially to generate the cobalt hydride intermediate involved in selective CO 2 reduction to formate. This work shows how to exploit kinetic basicity using ligand-cooperative design to facilitate PCET reactions involved in energy related transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids

Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. Here, we leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Mechanistic studies of a “Declick” reaction

A kinetic analysis of a “declick” reaction is described. Compound 1, previously reported to couple an amine and a thiol (i.e. “click”) under mild aqueous conditions to create 2, undergoes release of the unaltered coupling partners upon triggering with dithiothreitol (DTT). In the study reported herein various aniline derivatives possessing para-electron donating and withdrawing groups were used as the amines. UV/vis spectroscopy of the declick reaction shows time-dependent spectra lacking isosbestic points, implying a multi-step mechanism. Global data fitting using numerical integration of rate equations and singular value decomposition afforded the spectra and time-dependence of each species, as well as rate constants for each step. The kinetic analysis reveals a multi-step process with an intermediate where both thiols of DTT have added prior to expulsion of the aniline leaving group, followed by rearrangement to the final product. Hammett plots show a negative rho value on two of the steps, indicating positive charge building (i.e. reduction of a negative charge) in the step leading to the intermediate and its ratedetermining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Inelastic partial {gamma}-ray cross sections of {sup 150}Sm+n reactions for E{sub n} = 1-15 MeV

The {sup 150}Sm(n,n'{gamma}) reaction was measured from E{sub n} = 1 to 15 MeV at the Los Alamos Neutron Science Cemter (LANSCE). The {gamma} rays were detected with the Compton-suppressed Germanium Array for Neutron Induced Excitations (GEANIE). Measured {gamma}-ray excitation functions were converted to partial {gamma}-ray cross sections, Twenty four individual {gamma}-rays up to E{sub x} = 1.8 MeV in {sup 150}Sm were measured. Results are compared with enhanced Hauser Feshbach model calculations: the spin distribution in the pre-equilibrium reaction is calculated with the quantum mechanical model of Feshbach, Kerman and Koonin. The particle transmission coefficients were calculated with two different global optical model potential parameter sets. We employed the coupled-channel optical model based on the soft rotor model and with spherical potential.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2018

Properties of advanced coupled-cluster Green's function

We present an extension of the analysis previously applied to the retarded part of the coupled cluster (CC) Green's function to its advanced part. In analogy to our earlier studies for the retarded part, we demonstrate that the advanced CC Green's function is expressed in terms of connected diagrams only, which is a direct consequence of algebraic form of equations satisfied by CC amplitudes. We also demonstrate that omega-derivatives of the advanced CC Green's function can be calculated analytically and can be expressed in terms of connected diagrams only. We analyze the structure of connected diagrams and the role of intermediate operators which satisfy electron affinity equation-of-motion CC type conditions.

electronic structure theory↗

DOE OSTI2017

Dynamics of the Bingham Canyon rock avalanches (Utah, USA) resolved from topographic, seismic, and infrasound data: Bingham Canyon Rock Avalanches

The 2013 Bingham Canyon Mine rock avalanches represent one of the largest cumulative landslide events in recorded U.S. history and provide a unique opportunity to test remote analysis techniques for landslide characterization. We combine aerial photogrammetry surveying, topographic reconstruction, numerical runout modeling, and analysis of broadband seismic and infrasound data to extract salient details of the dynamics and evolution of the multiphase landslide event. Our results reveal a cumulative intact rock source volume of 52 Mm 3 , which mobilized in two main rock avalanche phases separated by 1.5 h. We estimate that the first rock avalanche had 1.5–2 times greater volume than the second. Each failure initiated by sliding along a gently dipping (21°), highly persistent basal fault before transitioning to a rock avalanche and spilling into the inner pit. The trajectory and duration of the two rock avalanches were reconstructed using runout modeling and independent force history inversion of intermediate-period (10–50 s) seismic data. Intermediate- and shorter-period (1–50 s) seismic data were sensitive to intervals of mass redirection and constrained finer details of the individual slide dynamics. Back projecting short-period (0.2–1 s) seismic energy, we located the two rock avalanches within 2 and 4 km of the mine. Further analysis of infrasound and seismic data revealed that the cumulative event included an additional 11 smaller landslides (volumes ~10 4 –10 5 m 3 ) and that a trailing signal following the second rock avalanche may result from an air-coupled Rayleigh wave. These results demonstrate new and refined techniques for detailed remote characterization of the dynamics and evolution of large landslides.

58 GEOSCIENCES↗

DOE OSTI2023

Temporally Stable Supramolecular Polymeric Salts Enabling High-Performance 3D All-Aromatic Polyimide Lattices

Vat photopolymerization (VP) Additive Manufacturing (AM), in which UV light is selectively applied to cure photo-active polymers into complex geometries with micron-scale resolution, has a limited selection of aliphatic thermoset materials that exhibit relatively poor thermal performance. Ring-opening dianhydrides with acrylate-containing nucleophiles yielded diacrylate ester-dicarboxylic acids that enabled photo-active polyimide (PI) precursors, termed polysalts, upon neutralization with an aromatic diamine in solution. In situ FTIR spectroscopy coupled with a solution and photo-rheological measurements revealed a previously unknown time-dependent instability of 4,4'-oxydianiline (ODA) polysalts due to an aza-Michael addition. Replacement of the electron-donating ether-containing diamine with an electron withdrawing sulfone-containing monomer, e.g., 4,4'-diaminodiphenyl sulfone (DDS), prohibited the aza-Michael addition of the aromatic amine to the activated acrylate double bond. Novel DDS polysalt photocurable solutions are similarly analyzed and validated long-term stability, which enabled reproducible printing of polyimide organogel intermediates. Subsequent VP AM afforded 3-dimensional (3D) structures of intricate complexity and excellent surface finish, as demonstrated with scanning electron microscopy. In addition, the novel PMDA-HEA/DDS solution enabled the production of the first beam latticed architecture comprised of all-aromatic polyimide. Finally, the versatility of a polysalt platform for multi-material printing is further demonstrated by printing parts with alternating polysalt compositions.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Fatigue of Composite Materials Subjected to Variable Loadings

A model describing the fatigue behavior of composite materials under variable loadings is presented. The approach is based on a two-parameter model fulfilling the principal responses’ features of composite materials subjected to constant amplitude cyclic loadings. It is shown that when coupled with the equivalent residual strength assumption the model can describe the strength degradation of composite materials subjected to variable amplitude loadings without simplifications or substantial reductions of the loading spectrum. Compared to the linear Miner’s rule, the results highlight the importance of the sequence of loads and the approach discriminates the ascending, descending and random patterns. It is shown that for the case under study the ordered descending (high to low) sequence showed the worst scenario in terms of damage accumulation extent, while the random spectrum resulted in an intermediate response between ordered ascending and descending sequences.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Mineralogy-dependent sulfide oxidation via polysulfide and thiosulfate pathways during weathering of mixed-sulfide bearing mine waste rock

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O 2 and Fe 3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S 2– , $S_{2}O_{2}^{2–}$, S 8 , $S_{2}O_{3}^{2–}$, and $S_{2}O_{4}^{2–}$) in a weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S 8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S 8 and $S_{2}O_{3}^{2–}$), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

58 GEOSCIENCES↗

DOE OSTI2020

Block orbital-selective Mott insulators: A spin excitation analysis

We present a comprehensive study of the spin excitations—as measured by the dynamical spin structure factor S(q,ω)—of the so-called block-magnetic state of low-dimensional orbital-selective Mott insulators. We realize this state via both a multi-orbital Hubbard model and a generalized Kondo-Heisenberg Hamiltonian. Due to various competing energy scales present in the models, the system develops periodic ferromagnetic islands of various shapes and sizes, which are antiferromagnetically coupled. The 2×2 particular case was already found experimentally in the ladder material BaFe2Se3 that becomes superconducting under pressure. Here we discuss the electronic density as well as Hubbard and Hund coupling dependence of S(q,ω) using density matrix renormalization group method. Several interesting features were identified: (1) An acoustic (dispersive spin-wave) mode develops. (2) The spin-wave bandwidth establishes a new energy scale that is strongly dependent on the size of the magnetic island and becomes abnormally small for large clusters. (3) Optical (dispersionless spin excitation) modes are present for all block states studied here. In addition, a variety of phenomenological spin Hamiltonians have been investigated but none matches entirely our results that were obtained primarily at intermediate Hubbard U strengths. Our comprehensive analysis provides theoretical guidance and motivation to crystal growers to search for appropriate candidate materials to realize the block states, and to neutron scattering experimentalists to confirm the exotic dynamical magnetic properties unveiled here, with a rich mixture of acoustic and optical features.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Serial-femtosecond crystallography reveals how a phytochrome variant couples chromophore and protein structural changes

The photoreaction and commensurate structural changes of a chromophore within biological photoreceptors elicit conformational transitions of the protein promoting the switch between deactivated and activated states. We investigated how this coupling is achieved in a bacterial phytochrome variant, Agp2-PAiRFP2. Contrary to classical protein crystallography, which only allows probing (cryo-trapped) stable states, we have used time-resolved serial femtosecond x-ray crystallography (tr-SFX) and pump-probe techniques with various illumination and delay times with respect to photoexcitation of the parent Pfr state. Thus, structural data for seven time frames were sorted into groups of molecular events along the reaction coordinate. They range from chromophore isomerization to the formation of Meta-F, the intermediate that precedes the functional relevant secondary structure transition of the tongue. Structural data for the early events were used to calculate the photoisomerization pathway to complement the experimental data. Late events allow identifying the molecular switch that is linked to the intramolecular proton transfer as a prerequisite for the following structural transitions.

59 BASIC BIOLOGICAL SCIENCES↗